Use of wax emulsions for improvement of wood durability ... - TARA
Use of wax emulsions for improvement of wood durability ... - TARA
Use of wax emulsions for improvement of wood durability ... - TARA
Create successful ePaper yourself
Turn your PDF publications into a flip-book with our unique Google optimized e-Paper software.
Ejwwp425_source<br />
<strong>Use</strong> <strong>of</strong> <strong>wax</strong> <strong>emulsions</strong> <strong>for</strong> <strong>improvement</strong> <strong>of</strong><br />
<strong>wood</strong> <strong>durability</strong> and sorption properties<br />
Boštjan LESAR and Miha HUMAR*<br />
University <strong>of</strong> Ljubljana, Biotechnical Faculty, Department <strong>for</strong> <strong>wood</strong> science and<br />
technology<br />
Jamnikarjeva 101, SI 1000 Ljubljana, Slovenia<br />
miha.humar@bf.uni-lj.si<br />
Abstract:<br />
Waxes are used <strong>for</strong> treatment <strong>of</strong> <strong>wood</strong> surfaces <strong>for</strong> several decades predominately as surface<br />
treatments because they weakly penetrate into the <strong>wood</strong>. In order to overcome this issue, water<br />
<strong>emulsions</strong> were applied in the present experiment. Five water <strong>emulsions</strong> <strong>of</strong> various concentrations<br />
were used, namely montan <strong>wax</strong>, polyethylene, ethylene copolymer and oxidized polyethylene <strong>wax</strong>.<br />
Per<strong>for</strong>mance <strong>of</strong> <strong>wax</strong> treated beech (Fagus sylvatica) and Norway spruce (Picea abies) against<br />
white rot, brown rot and blue stain fungi was tested. In parallel, sorption properties <strong>of</strong> <strong>wax</strong> treated<br />
<strong>wood</strong> were determined. The treated specimens were more resistant to <strong>wood</strong> decay fungi.<br />
Polyethylene and oxidized polyethylene <strong>wax</strong> were found to be particularly efficient. Although this<br />
treatment does not improve resistance to blue stain fungi, it reduces the sorption <strong>of</strong> water.<br />
Die Verwendung von Wachsemulsionen zur Verbesserung der<br />
Dauerhaftigkeit und der Sorptionseigenschaften von Holz<br />
Zusammenfassung<br />
Seit Jahrzehnten werden Wachse fast ausschließlich zur Oberflächenbehandlung<br />
von Holz verwendet, weil sie nur schwach in das Holz eindringen. Um das<br />
Eindringverhalten zu verbessern, wurden in dieser Studie fünf verschiedene<br />
Wasseremulsionen in unterschiedlichen Konzentrationen verwendet, und zwar<br />
zwei Montanwachse, Polyethylen, Ethylen-Copolymer und oxidiertes<br />
Polyethylenwachs. Die Resistenz von wachsbehandeltem Buchenholz (Fagus<br />
sylvatica) und Fichtenholz (Picea abies) gegen Weißfäule-, Braunfäule- und<br />
Bläuepilze wurde untersucht. Daneben wurden die Sorptionseigenschaften von<br />
1
Ejwwp425_source<br />
wachsbehandeltem Holz bestimmt. Die behandelten Prüfkörper waren gegen Holz<br />
zerstörende Pilze resistenter, wobei sich Polyethylen und oxidiertes<br />
Polyethylenwachs als besonders wirksam erwiesen. Zwar wird mit dieser<br />
Behandlung die Resistenz gegen Bläue nicht verbessert, jedoch wird die<br />
Wasseraufnahme reduziert.<br />
1. Introduction<br />
Despite the fact that <strong>wood</strong> has been used <strong>for</strong> construction applications <strong>for</strong><br />
thousands <strong>of</strong> years, it remains one <strong>of</strong> the most important building materials. The<br />
first users <strong>of</strong> <strong>wood</strong> faced the same problem that people face nowadays. Wood is<br />
not durable in outdoors applications; there<strong>for</strong>e, it has to be protected in some way<br />
if used in such environment. In the pa st, most preservative solutions had biocidal<br />
properties and there<strong>for</strong>e, inhibited pest growth and development (Richardson<br />
1993). Future solutions <strong>for</strong> the <strong>improvement</strong> <strong>of</strong> the <strong>durability</strong> <strong>of</strong> <strong>wood</strong><br />
preservatives are designed differently. They change the structure <strong>of</strong> <strong>wood</strong> so that<br />
<strong>wood</strong> pests do not recognize it as food source (Tjeerdsma et al. 1998); or, <strong>wood</strong><br />
moisture content is kept so low that decay processes are no longer possible<br />
(Goethals and Stevens 1994). It is believed that <strong>wax</strong> <strong>emulsions</strong> can be used in<br />
such manner as well. Treatment <strong>of</strong> <strong>wood</strong> with resin/<strong>wax</strong> water-repellent<br />
<strong>for</strong>mulations greatly reduces the rate <strong>of</strong> water flow in the capillaries and<br />
significantly increases the dimensional stability <strong>of</strong> specimens exposed to wet<br />
conditions (Berninghausen et al. 2006, Kurt et al. 2008). The most important<br />
applications <strong>of</strong> <strong>wax</strong>es in <strong>wood</strong> industry are found in particleboard production.<br />
Paraffin <strong>emulsions</strong> are introduced to the particleboards reducing water uptake and<br />
improving dimensional stability (Amthor 1972, Deppe and Ernst 1996).<br />
Nowadays, <strong>wax</strong> <strong>emulsions</strong> are added to OSB boards <strong>for</strong> the same reason<br />
(Neimsuwan et al. 2008). However, there are reports that paraffin treatment can<br />
2
Ejwwp425_source<br />
reduce water capillary uptake in <strong>wood</strong> as well (Scholz et al. 2009). Furthermore,<br />
<strong>wax</strong> treated <strong>wood</strong> exhibited increased compression strength and hardness (Rapp et<br />
al. 2005). In addition, <strong>wax</strong> and oil emulsion additives are incorporated into<br />
aqueous <strong>wood</strong> preservatives to reduce checking and improve the appearance <strong>of</strong><br />
treated <strong>wood</strong> exposed outdoors as well (Evans et al. 2009).<br />
Montan and carnauba <strong>wax</strong>es are some <strong>of</strong> the possible water repellent agents to be<br />
applied in order to improve <strong>wood</strong> <strong>durability</strong> as they are among the most resistant<br />
<strong>wax</strong>es that <strong>for</strong>m thin films. Montan and carnauba <strong>wax</strong> as well as other <strong>wax</strong>es are<br />
almost non-toxic and are used <strong>for</strong> a variety <strong>of</strong> applications like <strong>for</strong> instance<br />
cosmetics (Anonymus 2005). Crude montan <strong>wax</strong> belongs to the group <strong>of</strong> naturally<br />
occurring <strong>wax</strong>es <strong>of</strong> vegetable origin such as carnauba <strong>wax</strong> or candelilla <strong>wax</strong>.<br />
Montan <strong>wax</strong> is fossilized vegetable <strong>wax</strong> extracted from lignites, principally from<br />
central German brown coal reserves west <strong>of</strong> the Elbe River. It is a mixture <strong>of</strong><br />
chemical compounds that can be divided into three substance groups: <strong>wax</strong>es,<br />
resins, and asphaltic substances. Just like existing vegetable hard <strong>wax</strong>es such as<br />
carnauba <strong>wax</strong>, the pure <strong>wax</strong> substance in montan <strong>wax</strong> consists mainly <strong>of</strong> esters <strong>of</strong><br />
long-chain acids with long-chain alcohols and free long-chain acids. Other<br />
components such as free <strong>wax</strong> alcohols or ketones, paraffins or terpenes are usually<br />
present in small quantities (Matthies 2001). Wax is soluble in many organic<br />
solvents, particularly aromatic or chlorinated hydrocarbons, even under moderate<br />
heating. Montan <strong>wax</strong> is used in the <strong>for</strong>m <strong>of</strong> flakes, powders, pastes with solvents,<br />
or aqueous <strong>emulsions</strong> (Heinrichs 2003). One <strong>of</strong> the most important advantages <strong>of</strong><br />
montan <strong>wax</strong> is its capability to <strong>for</strong>m thin-layer resistant films (Warth 1959). One<br />
<strong>of</strong> the objects <strong>of</strong> this study was to show that this thin film could limit water<br />
penetration and as such improve per<strong>for</strong>mance against <strong>wood</strong> decay fungi. There are<br />
also other <strong>wax</strong>es - beside montan <strong>wax</strong> - used <strong>for</strong> the protection <strong>of</strong> concrete against<br />
3
Ejwwp425_source<br />
stains, particularly polyethylene, ethylene copolymer and oxidized polyethylene<br />
<strong>wax</strong>. Some <strong>of</strong> those <strong>wax</strong>es are already being used <strong>for</strong> car and plastic polishing<br />
(Erhuai 2008), as they protect the surface against salt, dust and other pollutants.<br />
Another important application is the protection <strong>of</strong> concrete walls and facades<br />
against weathering, staining etc. It is believed that they can <strong>for</strong>m a film on the<br />
<strong>wood</strong> surface as well as cell lumen. This enables faster water removal and<br />
decreases water sorption and desorption which results in an improved dimensional<br />
stability <strong>of</strong> <strong>wood</strong>. Dry <strong>wood</strong> will be less susceptible to fungal decay. Until now,<br />
<strong>wax</strong> (bee and paraffin <strong>wax</strong>es) has predominately been used <strong>for</strong> surface coatings<br />
(Burger 2006). It was dissolved in an organic solvent or melted prior use.<br />
However, melted <strong>wax</strong>es are only <strong>of</strong> minor importance as they do not penetrate<br />
deeper into the <strong>wood</strong> and remain on the surface <strong>of</strong> the treated material <strong>for</strong> most <strong>of</strong><br />
the treatments. A second treatment <strong>of</strong> <strong>wood</strong> with melted <strong>wax</strong>es requires special<br />
equipment, it is expensive and there is an increased risk <strong>of</strong> fire (Scholz et al.<br />
2009). On the other hand, organic solvents are becoming less and less desired due<br />
to environmental issues. The authors` intention is to prepare <strong>wax</strong> <strong>emulsions</strong> which<br />
will penetrate deeper into the <strong>wood</strong> and, there<strong>for</strong>e, protect it against fungal decay.<br />
To the authors` knowledge nothing has been reported on <strong>wax</strong> use in the field <strong>of</strong><br />
<strong>wood</strong> protection.<br />
2. Material and methods<br />
Treatment solutions used<br />
For impregnation, five types <strong>of</strong> <strong>wax</strong> <strong>emulsions</strong> <strong>of</strong> various concentrations were<br />
used, namely two <strong>emulsions</strong> <strong>of</strong> montan <strong>wax</strong> (LGE, MW1), one emulsion <strong>of</strong><br />
polyethylene (WE1), one emulsion <strong>of</strong> ethylene copolymer (WE3) and one<br />
emulsion <strong>of</strong> oxidized polyethylene (WE6) <strong>wax</strong>. The solutions are commercially<br />
4
Ejwwp425_source<br />
available and produced by Samson (Slovenia) and BASF (Germany).<br />
Concentrations (dry content) and basic properties <strong>of</strong> the <strong>wax</strong> <strong>emulsions</strong> can be<br />
seen in Table 1. In order to elucidate the penetration <strong>of</strong> <strong>wax</strong> <strong>emulsions</strong> to <strong>wood</strong>en<br />
specimens, the uptake <strong>of</strong> <strong>emulsions</strong> and the retention <strong>of</strong> <strong>wax</strong>es were determined<br />
gravimetrically. For retention measurements, samples were dried at 103 °C <strong>for</strong> 24<br />
hours, and their masses were determined be<strong>for</strong>e and after impregnation, and then<br />
the retention was calculated. This gravimetrically determined retention <strong>of</strong> <strong>wax</strong><br />
was compared to the theoretical retention calculated from the uptake <strong>of</strong> solution<br />
and the concentration <strong>of</strong> <strong>wax</strong> in the emulsion.<br />
Wood decay test<br />
Resistance <strong>of</strong> <strong>wood</strong> impregnated with various <strong>wax</strong> <strong>emulsions</strong> against <strong>wood</strong> decay<br />
fungi was determined according to EN 113 procedure (EN 113:989). Specimens<br />
were treated with various <strong>wax</strong> <strong>emulsions</strong> prior fungal exposure (vacuum – 70<br />
mbar; 20 min; pressure – 9.5 bar; 60 min; vacuum – 70 mbar; 10 min), as can be<br />
seen in Table 1. Wax treated specimens were air dried <strong>for</strong> four weeks. Steam<br />
sterilized, impregnated and unimpregnated <strong>wood</strong> specimens were exposed to three<br />
brown rot (Antrodia vaillantii, Serpula lacrymans and Gloeophyllum trabeum)<br />
and three white rot fungi (Trametes versicolor, Pleurotus ostreatus and<br />
Hypoxylon fragi<strong>for</strong>me). Beech <strong>wood</strong> (Fagus sylvatica) specimens were exposed to<br />
white rot and Norway spruce (Picea abies) specimens to brown rot fungi. After 16<br />
weeks <strong>of</strong> fungal exposure, specimens were isolated and mass losses were<br />
gravimetrically determined and expressed in percentages.<br />
Blue stain and moulds test<br />
Scots pine (Pinus sylvestris) <strong>wood</strong> specimens were surface brushed with various<br />
<strong>wax</strong> <strong>emulsions</strong> (Table 2). Their resistance was determined according to EN 152-1<br />
5
Ejwwp425_source<br />
procedure (EN 152-1:1996). The uptake <strong>of</strong> <strong>wax</strong> <strong>emulsions</strong> was approximately<br />
200 g/m 2 . After brushing, samples were left to dry <strong>for</strong> 3 weeks. Half <strong>of</strong> the<br />
samples were exposed to blue stain fungi, while the other half was exposed to<br />
moulds <strong>for</strong> 6 weeks according to the requirements <strong>of</strong> EN 152-1:1996.<br />
Aureobasidium pullulans and Sclerophoma pithyophila were used to test blue<br />
stain organisms. Fusarium solani, Gliocladium viride, Penicillium expynsum, and<br />
Penicillium janthinellum were used <strong>for</strong> testing mould organisms. Resistance<br />
against disfiguring fungi was estimated visually according to EN 152-1:1996.<br />
Additionally, color change was determined as well and expressed in the CIELab<br />
color system.<br />
Sorption properties<br />
Only LGE emulsion was used <strong>for</strong> the determination <strong>of</strong> sorption properties. There<br />
were two types <strong>of</strong> tests per<strong>for</strong>med to determine sorption properties. In the first<br />
one, impregnated specimens were conditioned in water container or in a high<br />
humidity chamber, and their masses were monitored. In the second set <strong>of</strong><br />
experiments, a tensiometer was used.<br />
The first set <strong>of</strong> sorption experiments were per<strong>for</strong>med on Norway spruce <strong>wood</strong><br />
specimens (1.5 × 2.5 × 5.0 cm³) with end sealed (epoxy coating) axial surfaces.<br />
They were impregnated (vacuum – 70 mbar; 20 min; pressure – 9.5 bar; 60 min;<br />
vacuum – 70 mbar; 10 min) with LGE <strong>emulsions</strong> <strong>of</strong> two different concentrations,<br />
LGE 50 and LGE 100. After four weeks <strong>of</strong> air drying, specimens were oven dried<br />
(40 °C) <strong>for</strong> three days. Afterwards, half <strong>of</strong> the specimens were transferred to the<br />
chamber with a relative air humidity <strong>of</strong> 82%. The masses <strong>of</strong> the specimens were<br />
monitored daily <strong>for</strong> six weeks. The second half <strong>of</strong> the specimens were immersed<br />
in distilled water. The masses <strong>of</strong> the specimens were monitored <strong>for</strong> three weeks<br />
6
Ejwwp425_source<br />
after predetermined periods shown in Figure 2. All moisture contents given are<br />
based on dry mass with <strong>wax</strong>.<br />
In the second part <strong>of</strong> experiments, Norway spruce <strong>wood</strong> specimens <strong>of</strong> the<br />
following size 2.0 × 3.0 × 4.0 cm³ (T × R × A) were utilized. The measurements<br />
were carried out at room temperature (20 °C) at a RH <strong>of</strong> 40 – 50% on a Krüss<br />
Processor Tensiometer K100. Axial surfaces <strong>of</strong> the specimens were positioned<br />
such that in contact with water, and afterwards their masses were measured<br />
continuously <strong>for</strong> 200 s. Each curve in Figure 3 is an average value <strong>of</strong> 10<br />
measurements.<br />
3. Results and discussion<br />
Wax <strong>emulsions</strong> used <strong>for</strong> impregnation in this experiment had different dry<br />
contents. They varied between 5.3% (LGE 50) and 23.1% (MW1 50) (Table 2).<br />
The influence <strong>of</strong> dry content on the properties <strong>of</strong> the <strong>emulsions</strong>, predominately<br />
viscosity, is significant. However, viscosity is also influenced by other<br />
parameters. The highest viscosity was observed <strong>for</strong> the WE3 emulsion, where a<br />
considerably higher viscosity is reported compared to the other <strong>wax</strong>es with a<br />
similar or even higher dry content. All <strong>emulsions</strong> applied, with the exemption <strong>of</strong><br />
LGE, have a rather high viscosity. Their penetration is presumably more limited<br />
compared to the penetration <strong>of</strong> aqueous solutions. In general, no difference was<br />
observed between the uptakes <strong>of</strong> preservative solution <strong>for</strong> beech <strong>wood</strong> specimens.<br />
Those specimens in average retained 650 kg/m 3 <strong>of</strong> <strong>wax</strong> <strong>emulsions</strong>. However,<br />
considerably higher variations in retentions were observed <strong>for</strong> spruce <strong>wood</strong><br />
specimens. Specimens impregnated with LGE 50 <strong>wax</strong> emulsion retained 570<br />
kg/m 3 <strong>of</strong> emulsion, while parallel specimens that were treated with the WE6 50<br />
emulsion up to 340 kg/m 3 <strong>of</strong> <strong>wax</strong> emulsion was retained (Table 2). It is presumed<br />
7
Ejwwp425_source<br />
that the main reason <strong>for</strong> the observed effect could be a better impregnability <strong>of</strong><br />
beech <strong>wood</strong> compared to spruce <strong>wood</strong>. It seems that the ability to penetrate into<br />
spruce <strong>wood</strong> specimens is in tight correlation with the dry content <strong>of</strong> <strong>wax</strong><br />
<strong>emulsions</strong> applied. For specimens that were impregnated with <strong>emulsions</strong> <strong>of</strong><br />
higher concentration, lower uptakes <strong>of</strong> preservative solutions were determined<br />
than <strong>for</strong> parallel specimens preserved with <strong>emulsions</strong> with a lower dry content<br />
(Figure 1). Although the emulsion particles (disperse phase) are rather small (100<br />
nm), they are too big to penetrate into the cell wall. Lignified <strong>wood</strong> cell walls<br />
contain a nanocapillary network that is 1 – 10 nm in size (Fujino and Itoh 1998).<br />
There<strong>for</strong>e, <strong>wax</strong> is deposited in the cell lumen only (Lesar et al. 2008).<br />
The fact that particles in the emulsion are too big to penetrate into the cell wall is<br />
reflected in the differences between gravimetrically determined <strong>wax</strong> retentions<br />
and theoretical <strong>wax</strong> retentions calculated from the solution uptake and dry content<br />
(Table 2). These differences varied between 2% and 23% in beech <strong>wood</strong><br />
specimens and between 12% and 74% in spruce specimens. This result shows a<br />
better impregnability <strong>of</strong> beech <strong>wood</strong>. However, differences in retention are most<br />
evident in spruce specimens impregnated with the WE3 emulsion, where 73% less<br />
<strong>wax</strong> was determined than was presumed from the uptake <strong>of</strong> solutions. It is<br />
presumed that during the impregnation process, water penetrated deeper into the<br />
specimens while <strong>wax</strong> remained on the surface.<br />
A more important object <strong>of</strong> this research was to determine the effect <strong>of</strong> <strong>wax</strong><br />
treatment on per<strong>for</strong>mance against <strong>wood</strong> decay fungi. All <strong>wood</strong> decay fungi used<br />
in this experiment were vital, as mass losses <strong>of</strong> control specimens were higher<br />
than 20%, with the exception <strong>of</strong> A. vaillantii where control specimens only lost<br />
16.9%. This fungal strain is known as a less aggressive, but on the other hand very<br />
effective degrader <strong>of</strong> impregnated and modified <strong>wood</strong> (Table 3).<br />
8
Ejwwp425_source<br />
Mass losses <strong>of</strong> specimens impregnated with different <strong>wax</strong> <strong>emulsions</strong> varied from<br />
2% (WE6 50; T. versicolor) up to 32% (WE3 50; H. fragi<strong>for</strong>me). As seen in Table<br />
1, it can be concluded that applied <strong>wax</strong> <strong>emulsions</strong> can slow down <strong>wood</strong> fungi to<br />
grow. Among the treatments the WE3 <strong>wax</strong> emulsion (emulsion <strong>of</strong> ethylene<br />
copolymer <strong>wax</strong>) was found to be least effective. This emulsion was the most<br />
viscose one among the <strong>emulsions</strong> tested, and its penetration into the <strong>wood</strong>en<br />
specimens was the worst. It should be considered that most <strong>of</strong> the <strong>wax</strong> remained<br />
on the surface <strong>of</strong> the treated specimens and there<strong>for</strong>e did not have prominent<br />
influence on the per<strong>for</strong>mance <strong>of</strong> the impregnated <strong>wood</strong> (Table 2). Additionally,<br />
specimens impregnated with montan <strong>wax</strong> <strong>emulsions</strong> (LGE and MW) were<br />
decayed less than the control ones. Among the fungi tested, montan <strong>wax</strong><br />
<strong>emulsions</strong> were found to be the least effective ones against G. trabeum. During<br />
the 16 weeks <strong>of</strong> exposure to the fungi mentioned above, the control specimens lost<br />
35.7% while the specimens impregnated with montan <strong>wax</strong> <strong>emulsions</strong> lost between<br />
26.1% and 15.8% depending on the concentration <strong>of</strong> montan <strong>wax</strong> in <strong>emulsions</strong>.<br />
Specimens impregnated with <strong>emulsions</strong> <strong>of</strong> higher concentrations were better<br />
protected against <strong>wood</strong> decay fungi than specimens impregnated with lower<br />
concentrations <strong>of</strong> montan <strong>wax</strong> (Table 3). Among the tested <strong>wax</strong> <strong>emulsions</strong>,<br />
<strong>emulsions</strong> WE1 (emulsion <strong>of</strong> polyethylene <strong>wax</strong>) and WE6 (emulsion <strong>of</strong> oxidized<br />
polyethylene <strong>wax</strong>) proved to be the most effective agents <strong>for</strong> the protection <strong>of</strong><br />
<strong>wood</strong> against <strong>wood</strong> rotting fungi. For example, after 16 weeks <strong>of</strong> exposure to G.<br />
trabeum, mass losses <strong>of</strong> spruce <strong>wood</strong> specimens impregnated with the WE1 50<br />
emulsion were only 3.8% and 5.7% after exposure to S. lacrymans. This treatment<br />
was effective against white rot species as well. P. ostreatus caused mass loss <strong>of</strong><br />
8.4%, while T. versicolor decayed only 3.9% <strong>of</strong> impregnated specimens (Table 3).<br />
Un<strong>for</strong>tunately, WE1 and WE6 <strong>emulsions</strong> were not that effective against A.<br />
9
Ejwwp425_source<br />
vaillantii and H. fragi<strong>for</strong>me. A comparison <strong>of</strong> the dry content data and mass losses<br />
after fungal decay revealed that there is no statistically significant correlation<br />
between those two parameters. This indicates that fungicidal properties <strong>of</strong><br />
impregnated <strong>wood</strong> depend more on the properties <strong>of</strong> <strong>wax</strong> than those <strong>of</strong> dry<br />
content. pH is one <strong>of</strong> the mechanisms which could explain the efficacy <strong>of</strong> the <strong>wax</strong><br />
treated <strong>wood</strong>. Wood treated with <strong>wax</strong> <strong>emulsions</strong> WE1 and WE6 with pH around 9<br />
exhibited a better per<strong>for</strong>mance against <strong>wood</strong> decay fungi than montan <strong>wax</strong> treated<br />
<strong>wood</strong>. It is well known that fungi prefer slightly acidic substrates rather than<br />
alkaline ones (Schmidt 2006). However, resistance <strong>of</strong> <strong>wax</strong> treated <strong>wood</strong> to <strong>wood</strong><br />
decay fungi cannot be explained by pH dependent mechanisms, as <strong>wax</strong> emulsion<br />
WE3 has alkaline pH, but fungi can degrade WE3 treated <strong>wood</strong> to similar extent<br />
to the LGE ones. The other mechanism that potentially improves the per<strong>for</strong>mance<br />
<strong>of</strong> the <strong>wax</strong> treated <strong>wood</strong> against <strong>wood</strong> decay fungi is film/barrier <strong>for</strong>med in the<br />
cell lumina and on the surface <strong>of</strong> the specimens. This barrier slows down<br />
moisturizing, the diffusion <strong>of</strong> enzymes and degradation products between hyphen<br />
and <strong>wood</strong>. It is presumed that this mechanism only slows down the degradation<br />
processes and does not stop them. There<strong>for</strong>e it is suggested that the EN 113 test<br />
should be prolonged to overcome the influence <strong>of</strong> a slow down diffusion. This<br />
experimental issue is overcome in long lasting field tests. The preliminary results<br />
<strong>of</strong> the double layer field trial showed that after two and a half years <strong>of</strong> natural<br />
exposure there is considerable decay at the control unimpregnated spruce <strong>wood</strong><br />
specimens. After eight months <strong>of</strong> exposure, the first fruiting bodies <strong>of</strong> the<br />
Gloeophyllum sp. were noticed. On the other hand, there were no signs <strong>of</strong> decay<br />
on the parallel spruce <strong>wood</strong> treated with LGE, WE1 or WE6 <strong>emulsions</strong>. This is<br />
additional evidence that <strong>wax</strong> treated <strong>wood</strong> exhibits a better per<strong>for</strong>mance against<br />
<strong>wood</strong> decay fungi than untreated <strong>wood</strong>. As already explained, the authors believe<br />
10
Ejwwp425_source<br />
that the most important reason <strong>for</strong> improved per<strong>for</strong>mance <strong>of</strong> <strong>wax</strong> treated <strong>wood</strong> in<br />
double layers is due to moisture relating effects. Moisture content <strong>of</strong> <strong>wax</strong> treated<br />
<strong>wood</strong> was lower. There<strong>for</strong>e they are les susceptible to decay.<br />
Un<strong>for</strong>tunately, <strong>wax</strong> <strong>emulsions</strong> do not improve the resistance <strong>of</strong> <strong>wax</strong> treated <strong>wood</strong><br />
against blue stain and mould fungi. Both control and impregnated specimens were<br />
completely stained after blue stain exposure as well as after exposure to moulds.<br />
The surface <strong>of</strong> the specimens was covered with stains that covered more than 60%<br />
<strong>of</strong> the surface (Table 4). Despite the fact that both specimens exposed to blue<br />
stains and moulds were estimated with the same mark (3), the color change (ΔE)<br />
that can be seen in Table 4 clearly shows that control specimens exposed to the<br />
blue stain fungi were considerably darker than the ones exposed to mould fungi. A<br />
similar effect can be observed <strong>for</strong> impregnated specimens as well. Un<strong>for</strong>tunately,<br />
none <strong>of</strong> the <strong>wax</strong> <strong>emulsions</strong> improved the resistance <strong>of</strong> the treated <strong>wood</strong> against<br />
staining organisms. A visual estimation showed some traces <strong>of</strong> inhibitory<br />
properties. All <strong>wax</strong> <strong>emulsions</strong>, with the exception <strong>of</strong> WE3, slightly inhibit<br />
moulding. This effect was not expressed <strong>for</strong> all specimens but only <strong>for</strong> some <strong>of</strong><br />
them. The effect <strong>of</strong> <strong>wax</strong>es against blue staining was even less prominent. The<br />
color analysis <strong>of</strong> the <strong>wax</strong> treated specimens exposed to staining fungi showed an<br />
even more negative influence <strong>of</strong> <strong>wax</strong>es on the resistance against staining. This<br />
analysis showed that there might be fewer individual stains on the surface <strong>of</strong> the<br />
specimens, and there was less surface covered with stains, but those stains were<br />
darker than the stains on control specimens. There might be a better resistance <strong>of</strong><br />
<strong>wax</strong> treated <strong>wood</strong> observed if the specimens had been impregnated instead <strong>of</strong><br />
surface treated.<br />
11
Ejwwp425_source<br />
The impregnation <strong>of</strong> spruce <strong>wood</strong> with <strong>wax</strong>es has an effect on sorption properties<br />
<strong>of</strong> impregnated <strong>wood</strong> as well. An increase <strong>of</strong> the moisture content <strong>of</strong> the LGE<br />
impregnated specimens was slower compared to the specimens conditioned in<br />
humid air as well as the ones immersed in water. The moisture content (MC) <strong>of</strong><br />
<strong>wood</strong> impregnated with the LGE emulsion after 60 days <strong>of</strong> conditioning was also<br />
lower than the MC <strong>of</strong> control specimens. It can be seen from Figure 2a that the<br />
MC <strong>of</strong> LGE 100 impregnated specimens at RH <strong>of</strong> 80% was 12.1%, while an 15%<br />
higher moisture content was observed <strong>for</strong> the control specimens after 60 days <strong>of</strong><br />
conditioning. The MC mentioned above was even reached after 18 days <strong>for</strong><br />
control specimens. It can be seen in Figure 2a that even after 60 days <strong>of</strong><br />
conditioning <strong>of</strong> specimens impregnated with the LGE 100 emulsion, they did not<br />
reach their equilibrium moisture content. The MC <strong>of</strong> LGE treated specimens was<br />
still slightly increasing even after two months <strong>of</strong> conditioning. This indicates that<br />
the LGE <strong>wax</strong> can <strong>for</strong>m a film on <strong>wood</strong> that is able to significantly slow down the<br />
adsorption. A similar effect was observed during the wetting <strong>of</strong> <strong>wood</strong>en<br />
specimens (Figure 2b). The uptake <strong>of</strong> water <strong>of</strong> specimens impregnated with LGE<br />
<strong>emulsions</strong> was slower than that <strong>of</strong> control specimens. The final MC <strong>of</strong> control<br />
specimens was 96%, while LGE impregnated specimens absorbed approximately<br />
17% less water. It is presumed that there are three reasons <strong>for</strong> this. Firstly, <strong>wax</strong>ing<br />
makes the surface <strong>of</strong> the specimens more hydrophobic. Secondly, the cell lumina<br />
were at least partly filled with <strong>wax</strong>es and this physically prevents moisturizing.<br />
Finally, there were thin film-barriers <strong>for</strong>med on the surface <strong>of</strong> the <strong>wood</strong>en<br />
specimens, which slow down water movement.<br />
This hydrophobic effect <strong>of</strong> the montan <strong>wax</strong> can also be seen from the<br />
measurement <strong>of</strong> the water uptake using tensiometer (Figure 3). During this test,<br />
12
Ejwwp425_source<br />
axial surfaces <strong>of</strong> <strong>wood</strong>en specimens were positioned such that in contact with<br />
water. Afterwards, the water uptake was gravimetrically measured. The uptake <strong>of</strong><br />
water in control spruce <strong>wood</strong> specimens was relatively fast. Within 200 s,<br />
specimens from axial surfaces (6 cm 2 ) retained more than 0.8 g <strong>of</strong> water. The<br />
shape <strong>of</strong> the uptake is clearly logarithmical. The uptake <strong>of</strong> water is faster in the<br />
beginning and then slows down. Approximately half <strong>of</strong> the water was absorbed<br />
after 30 s (Figure 3). The water uptake in the montan <strong>wax</strong> impregnated specimens<br />
was considerably lower <strong>for</strong> both specimens impregnated with pure LGE emulsion<br />
(LGE 100) and <strong>for</strong> the ones impregnated with the same emulsion <strong>of</strong> a lower<br />
concentration (LGE 50). The shape <strong>of</strong> the water uptake curve <strong>for</strong> LGE treated<br />
specimens significantly differs from the curve observed <strong>for</strong> control specimens.<br />
The water uptake decreased during the initial stage. It reached its maximum after<br />
12 s (LGE 100) or 16 s (LGE 50), and then appeared to decrease rapidly be<strong>for</strong>e it<br />
started increasing again after 50 s (Figure 3). This pattern is characteristic <strong>for</strong><br />
hydrophobic surfaces (Rowel and Banks 1985). There was no decrease in the<br />
water uptake, but this pattern is a result <strong>of</strong> the hydrophobic properties and the<br />
lifting power <strong>of</strong> the water in contact with the surface where contact angles are<br />
higher than 90 degrees. However, after 200 s the LGE 50 treated spruce<br />
specimens took eight times less water up than the control ones, while the uptake<br />
in LGE 100 treated <strong>wood</strong> was even lower. This is an additional pro<strong>of</strong> that montan<br />
<strong>wax</strong> treatment improves the sorption properties <strong>of</strong> <strong>wax</strong> treated <strong>wood</strong>.<br />
4. Conclusion<br />
The uptake <strong>of</strong> <strong>wax</strong> emulsion based solutions in spruce <strong>wood</strong> specimens was<br />
influenced by dry content and viscosity <strong>of</strong> the <strong>wax</strong> <strong>emulsions</strong> applied. Some <strong>of</strong> the<br />
<strong>wax</strong> <strong>emulsions</strong> tested do considerably slow down fungal degradation, but do not<br />
13
Ejwwp425_source<br />
stop it. Emulsions <strong>of</strong> oxidized polyethylene <strong>wax</strong> (WE6) were found to be<br />
particularly effective. Un<strong>for</strong>tunately, treatment <strong>of</strong> <strong>wood</strong> with <strong>wax</strong>es does not<br />
prevent staining. One <strong>of</strong> the positive properties <strong>of</strong> treated <strong>wood</strong> is that the<br />
impregnation <strong>of</strong> <strong>wood</strong> with emulsion <strong>of</strong> montan <strong>wax</strong> reduces water uptake <strong>of</strong> the<br />
<strong>wax</strong> treated <strong>wood</strong>. It is believed that <strong>wax</strong> <strong>emulsions</strong> have the potential to be used<br />
<strong>for</strong> <strong>wood</strong> protection in less hazardous outdoor applications.<br />
5. Acknowledgements<br />
The authors would like to acknowledge the Slovenian Research Agency <strong>for</strong> financial support in<br />
the frame <strong>of</strong> the projects L4-0820-0481 and P4-0015-048. We appreciate the technical support <strong>of</strong><br />
Gregor Smrdelj, Žiga Melanšek and Jože Avguštinčič.<br />
6. References<br />
Amthor J (1972) Paraffin dispersions <strong>for</strong> waterpro<strong>of</strong>ing <strong>of</strong> particle board. Holz Roh- Werkst.<br />
30(11): 422-425<br />
Anonymus (2005) Poligen MW1, Technical in<strong>for</strong>mation. www.basf.de, Accessed 2.10.2008<br />
Berninghausen CG, Rapp AO, Welzbacher CR. (2006) Impregnating agent, process <strong>for</strong><br />
impregnating <strong>of</strong> dried and pr<strong>of</strong>iled <strong>wood</strong>, and <strong>wood</strong> product impregnated therewith, patent<br />
EP1660285<br />
Burger HJ (2006) Method <strong>for</strong> introducing <strong>wax</strong> in thermal <strong>wood</strong>, patent EP1646483<br />
Evans PD, Wingate-Hill R, Cunningham RS. (2009) Wax and oil emulsion additives: How<br />
effective are they at improving the per<strong>for</strong>mance <strong>of</strong> preservative-treated <strong>wood</strong>? Forest Prod J. 59(1-<br />
2): 66-70<br />
Erhuai L (2008) Wax polish and preparation method there<strong>of</strong>, patent CN101148565<br />
European Committee <strong>for</strong> Standardization EN 113 (1989). Wood preservatives; Determination <strong>of</strong><br />
the toxic values against <strong>wood</strong> destroying basidiomycetes cultured an agar medium<br />
European Committee <strong>for</strong> standardization EN 152-1 (1996) Test methods <strong>for</strong> determining the<br />
protective effectiveness <strong>of</strong> a preservative treatment against blue stain in service – Part 1: Brushing<br />
procedure<br />
Fujino T, Itoh T (1998) Changes in the three dimensional architecture <strong>of</strong> the cell wall during<br />
lignification <strong>of</strong> xylem cells in Eucalyptus tereticornis. Holz<strong>for</strong>schung 52: 111–116<br />
Goethals P, Stevens M (1994) Dimensional stability and decay resistance <strong>of</strong> <strong>wood</strong> upon<br />
modification with some new type chemical reactants. The International Research Group on Wood<br />
Preservation, Document, IRG/WP 94-40028, p. 14<br />
14
Ejwwp425_source<br />
Heinrichs FL (2003) Montan <strong>wax</strong>. In: Bhonet M. (ed) Ullman’s encyclopedia <strong>of</strong> industrial<br />
chemistry, Vol. 39 –chapter 3. Eds. Wiley-VCH, Weinheim, pp. 154-159.<br />
Kurt R, Krause A, Militz H, Mai C (2008) Hydroxymethylated resorcinol (HMR) priming agent<br />
<strong>for</strong> improved bondability <strong>of</strong> <strong>wax</strong>-treated <strong>wood</strong>. Holz Roh- Werkst. 66(5):333-338.<br />
Lesar B, Zupančič M, Humar M (2008) Microscopic analysis <strong>of</strong> <strong>wood</strong> impregnated with aqueous<br />
montan <strong>wax</strong> emulsion. LesWood 60(9): 320-326.<br />
Matthies L. (2001) Natural montan <strong>wax</strong> and its raffinates. Eur J <strong>of</strong> Lipid Sci and Tech; 103:239-<br />
248.<br />
Neimsuwan T, Wang S, Via BK. (2008) Effect <strong>of</strong> processing parameters, resin, and <strong>wax</strong> loading<br />
on water vapor sorption <strong>of</strong> <strong>wood</strong> strands. Wood Fiber Sci 40(4): 495-504<br />
Rapp AO, Beringhausen C, Bollmus S, Brischke C, Frick T, Haas T, Sailer M, Welzbacher CR.<br />
(2005) Hydrophobierung von Holz-Erfahrungen nach 7 Jahren Freilandtest. In: 24th<br />
Holzschutztagung der DGFH, Leipzig, Germany, 157-170.<br />
Richardson BA (1993) Wood Preservation. Second edition. E & FN Spon, London, Glasgow<br />
Rowell RM, Banks WB (1985) Water Repellency and Dimensional Stability <strong>of</strong> Wood. Madison<br />
U.S. Forest Products Laboratory. FPL 50-RP. pp. 24<br />
Schmidt O. (2006) Wood and Tree Fungi Biology, Damage, Protection, and <strong>Use</strong>. Springer Berlin<br />
Heidelberg, New York, pp. 329<br />
Scholz G, Krause A, Militz H. (2009) Capillary Water Uptake and Mechanical Properties <strong>of</strong> Wax<br />
Soaked Scots Pine.in: 4 th European Conference on Wood Modification, Stockholm, pp. 209- 212<br />
Tjeerdsma BF, Boonstra M, Militz H, (1998) Thermal modification <strong>of</strong> non-durable <strong>wood</strong> species<br />
2. Improved <strong>wood</strong> properties <strong>of</strong> thermally treated <strong>wood</strong>. The International Research Group on<br />
Wood Preservation, Document, IRG/WP 98-40124, p. 10<br />
Warth AH (1959) The chemistry and Technology <strong>of</strong> Waxes. Reinhold Publishing Corporation,<br />
New York (USA)<br />
15
Ejwwp425_source<br />
600<br />
Uptake <strong>of</strong> <strong>wax</strong> emulsion (kg/m 3 )<br />
550<br />
500<br />
450<br />
400<br />
350<br />
r ²0.71<br />
300<br />
0 5 10 15 20 25<br />
Dry content <strong>of</strong> emulsion (%)<br />
Figure 1: Correlation between dry contents <strong>of</strong> the emulsion and uptake <strong>of</strong><br />
preservative solutions in spruce <strong>wood</strong> specimens<br />
16
Ejwwp425_source<br />
14<br />
12<br />
a<br />
10<br />
MC (%)<br />
8<br />
6<br />
4<br />
2<br />
0<br />
control<br />
LGE 50<br />
LGE 100<br />
0 10 20 30 40 50 60<br />
Time (day)<br />
120<br />
100<br />
b<br />
80<br />
MC (%)<br />
60<br />
40<br />
20<br />
0<br />
control<br />
LGE 50<br />
LGE 100<br />
0 100 200 300 400 500 600<br />
Time (h)<br />
Figure 2: Changes in moisture contents (MC) <strong>of</strong> the control specimens and<br />
specimens treated with LGE <strong>wax</strong> <strong>emulsions</strong> in atmosphere with RH <strong>of</strong> 82% (a)<br />
or during immersion in water (b).<br />
17
Ejwwp425_source<br />
1,0<br />
0,8<br />
Control<br />
LGE 50<br />
LGE 100<br />
Water uptake (g)<br />
0,6<br />
0,4<br />
0,2<br />
0,0<br />
-0,2<br />
0 50 100 150 200<br />
Time (s)<br />
Figure 3: Water uptake <strong>of</strong> axial surfaces <strong>of</strong> the montan <strong>wax</strong> (LGE) and control<br />
specimens expressed in grams. Uptake was determined with tensiometer.<br />
18
Ejwwp425_source<br />
Table 1: Selected properties <strong>of</strong> the undiluted/commercial <strong>wax</strong> <strong>emulsions</strong> used<br />
Preservative<br />
solution<br />
Dry<br />
content<br />
(%)<br />
pH<br />
Emulsion<br />
viscosity<br />
(4 mm 23 °C)<br />
ISO 2431<br />
(s)<br />
Density<br />
(g/m 3 )<br />
Melting<br />
point <strong>of</strong><br />
solids (°C)<br />
Average<br />
particle<br />
size (nm)<br />
LGE 11.4 5.5 13 1.00 76 – 80 100 n.a.<br />
Emulsifier system<br />
MW1 46.2 4.6 25 1.01 78 100 Nonionic<br />
WE1 36.4 9.9 20 – 36 1.00 130 – 135 100 Nonionic/anionic<br />
WE3 28.4 9.7 85* 1.00 85 100 n.a.<br />
WE6 38.2 8.9 20 – 60 1.00 126 – 133 100 Nonionic/anionic<br />
19
Ejwwp425_source<br />
Table 2: Uptake <strong>of</strong> <strong>wax</strong> <strong>emulsions</strong> during impregnation process with regard to<br />
concentration, <strong>wood</strong> species and composition <strong>of</strong> solution. In addition, there are<br />
gravimetrically determined retention and differences between theoretically<br />
calculated and actual retention.<br />
Wax<br />
emulsion<br />
LGE<br />
MW1<br />
WE1<br />
WE3<br />
WE6<br />
Spruce <strong>wood</strong><br />
Beech <strong>wood</strong><br />
Difference<br />
Difference<br />
between<br />
between<br />
Conc. Dry<br />
Uptake <strong>of</strong><br />
Uptake <strong>of</strong> Retention theoretical<br />
Retention theoretical<br />
(%) cont. (%)<br />
<strong>wax</strong><br />
<strong>wax</strong> emulsion <strong>of</strong> <strong>wax</strong> and actual<br />
<strong>of</strong> <strong>wax</strong> and actual<br />
(kg/m 3 ) (kg/m 3 emulsion<br />
) <strong>wax</strong><br />
(kg/m 3 (kg/m 3 ) <strong>wax</strong><br />
)<br />
retention<br />
retention<br />
(%)<br />
(%)<br />
50 5.3 555 26 12 644 34 2<br />
100 11.4 386 32 27 647 67 10<br />
25 10.9 441 41 16 639 58 17<br />
50 23.1 347 53 34 662 126 18<br />
25 9.4 500 39 16 641 56 6<br />
50 18.2 370 52 24 668 113 7<br />
25 7.3 569 30 29 659 40 17<br />
50 14.2 494 18 74 663 72 23<br />
25 9.4 462 35 19 655 56 9<br />
50 19.1 340 45 31 670 110 14<br />
20
Ejwwp425_source<br />
Wax<br />
emulsion<br />
LGE<br />
MW1<br />
WE1<br />
WE3<br />
WE6<br />
Table 3: Mass loss <strong>of</strong> the <strong>wax</strong> treated spruce and beech <strong>wood</strong> specimens exposed<br />
to various <strong>wood</strong> decay fungi according to EN 113 procedure.<br />
Wood decay fungi<br />
Conc.<br />
(%)<br />
G. trabeum A.<br />
vaillantii<br />
S. lacrymans P. ostreatus T.<br />
versicolor<br />
H. fragi<strong>for</strong>me<br />
Mass loss (%)<br />
50 26.1 11.2 18.8 15.2 24.6 28.5<br />
100 24.7 14.8 17.8 11.4 20.4 23.7<br />
25 22.2 10.4 17.2 13.2 21.4 24.4<br />
50 15.8 11.7 13.1 7.3 13.9 20.7<br />
25 6.0 7.3 12.2 14.8 20.8 30.9<br />
50 3.8 10.9 5.7 8.4 3.9 18.3<br />
25 21.2 16.1 27.4 13.7 30.6 27.6<br />
50 13.6 16.2 30.0 20.4 22.3 32.4<br />
25 23.0 11.3 7.1 10.0 17.9 22.4<br />
50 7.7 7.8 3.2 8.9 1.6 21.7<br />
Control / 35.7 16.9 40.2 23.0 32.0 32.7<br />
21
Ejwwp425_source<br />
Table 4: Resistance <strong>of</strong> pine <strong>wood</strong> specimens to blue stain and mould fungi<br />
determined according to EN 152-1 procedure.<br />
Wax<br />
emulsion<br />
Conc.<br />
(%)<br />
Visual<br />
estimation<br />
-<br />
moulds<br />
Visual<br />
estimation<br />
-<br />
blue stain<br />
ΔE - Color change<br />
after exposure to<br />
moulds<br />
ΔE - Color change after<br />
exposure to blue stain<br />
fungi<br />
LGE 50 2.8 3 13.1 40.2<br />
100 2.4 2.8 12.0 39.8<br />
MW A 25 2.3 3 8.3 32.9<br />
50 2.4 3 8.3 39.2<br />
WE 1 A 25 2.4 3 11.1 29.2<br />
50 2.9 2.6 12.2 21.1<br />
WE 3 A 25 3 2.8 18.1 27.7<br />
50 3 3 18.6 41.6<br />
WE 6 A 25 2.6 2.6 12.0 32.9<br />
50 2.25 3 27.2 32.3<br />
Control / 3 3 9.1 25.9<br />
22
Ejwwp425_source<br />
Abb. 1<br />
Korrelation zwischen Trockengehalt der Emulsion und Schutzmittelaufnahme in<br />
Fichtenholzprüfkörpern<br />
Abb. 2<br />
Änderung der Holzfeuchte (MC) der Kontrollproben und der mit LGE<br />
Wachsemulsionen behandelten Prüfkörper a) in einer Umgebung von 82% rel.Lf.<br />
oder b) bei Wasserlagerung<br />
Abb. 3<br />
Wasseraufnahme über die Hirnholzflächen von mit Montanwachs (LGE)<br />
behandelten sowie Kontrollproben, in Gramm. Die Wasseraufnahme wurde mit<br />
einem Tensiometer gemessen.<br />
Tabelle 1<br />
Verschiedene Eigenschaften der verwendeten unverdünnten/handelsüblichen<br />
Wachsemulsionen<br />
Tabelle 2<br />
Aufnahme von Wachsemulsionen während der Imprägnierung in Abhängigkeit<br />
von der Konzentration, der Holzart und der Zusammensetzung der Lösung.<br />
Zusätzlich sind die gravimetrisch bestimmte Einbringmenge sowie die<br />
Unterschiede zwischen theoretisch berechneter und tatsächlicher Einbringmenge<br />
angegeben.<br />
Tabelle 3<br />
Masseverluste der wachsbehandelten Fichten- und Buchenholzprüfkörper nach<br />
Befall mit verschiedenen Holz zerstörenden Pilzen gemäß EN 113.<br />
Tabelle 4<br />
Resistenz der Kiefernholzprüfkörper gegen Bläue und Schimmelpilze gemäß EN<br />
152-1 bestimmt<br />
23